Thin film diode integrated with chalcogenide memory cell

ABSTRACT

An integrated programmable conductor memory cell and diode device in an integrated circuit comprises a diode and a glass electrolyte element, the glass electrolyte element having metal ions mixed or dissolved therein and being able to selectively form a conductive pathway under the influence of an applied voltage. In one embodiment, both the diode and the memory cell comprise a chalcogenide glass, such as germanium selenide (e.g., Ge 2 Se 8  or Ge 25 Se 75 ). The first diode element comprises a chalcogenide glass layer having a first conductivity type, the second diode element comprises a chalcogenide glass layer doped with an element such as bismuth and having a second conductivity type opposite to the first conductivity type and the memory cell comprises a chalcogenide glass element with silver ions therein. In another embodiment, the diode comprises silicon and there is a diffusion barrier layer between the diode and the chalcogenide glass memory element. Methods of fabricating integrated programmable conductor memory cell and diode devices are also disclosed.

FIELD OF THE INVENTION

[0001] This invention relates generally to a method of manufacture for memory devices in integrated circuits and more particularly to programmable conductor memory arrays comprising glass electrolyte elements.

BACKGROUND OF THE INVENTION

[0002] The digital memory most commonly used in computers and computer system components is the dynamic random access memory (DRAM), wherein voltage stored in capacitors represents digital bits of information. Electric power must be supplied to the capacitors to maintain the information because, without frequent refresh cycles, the stored charge dissipates, and the information is lost. Memories that require constant power are known as volatile memories.

[0003] Non-volatile memories do not need frequent refresh cycles to preserve their stored information, so they consume less power than volatile memories and can operate in an environment where the power is not always on. There are many applications where non-volatile memories are preferred or required, such as in cell phones or in control systems of automobiles. Non-volatile memories include magnetic random access memories (MRAMs), erasable programmable read only memories (EPROMs) and variations thereof.

[0004] Another type of non-volatile memory is the programmable conductor or programmable metallization memory cell, which is described by Kozicki et al. in (U.S. Pat. No. 5,761,115; No. 5,914,893; and No. 6,084,796) and is included by reference herein. The programmable conductor cell of Kozicki et al. (also referred to by Kozicki et al. as a “metal dendrite memory”) comprises a glass ion conductor, such as a chalcogenide-metal ion glass and a plurality of electrodes disposed at the surface of the fast ion conductor and spaced a distance apart from one another. The glass/ion element shall be referred to herein as a “glass electrolyte,” or, more generally, “cell body.”

[0005] When a voltage is applied to the anode and the cathode, a non-volatile conductive pathway (considered a sidewall “dendrite” by Kozicki et al.) grows from the cathode through or along the cell body towards the anode, shorting the electrodes and allowing current flow. The dendrite stops growing when the voltage is removed. The dendrite shrinks, re-dissolving metal ions into the cell body, when the voltage polarity is reversed. In a binary mode, the programmable conductor cell has two states; a fully-grown dendrite or shorted state that can be read as a 1, and a state wherein the dendrite does not short out the electrodes that can be read as a 0, or vice versa. It is also possible to arrange variable resistance or capacitance devices with multiple states.

[0006] The recent trends in memory arrays generally have been to form first a via, then fill it with a memory storage element (e.g., capacitor) and etch back. It is simple to isolate individual memory cells in this way. Programmable memory cells also have been fabricated using this so-called container configuration, wherein the electrodes and cell body layers are deposited into a via that has been etched into an insulating layer. Metal diffusion in the course of growing and shrinking the conductive pathway is confined by the via wall. The memory cell can be formed in a number of array designs. For example, in a cross-point circuit design, memory elements are formed between upper and lower conductive lines at intersections. When forming a programmable conductor array with the glass electrolyte elements similar to those of Kozicki et al., vias are formed in an insulating layer and filled with the memory cell bodies, such as metal-doped glass electrolyte or glass fast ion diffusion (GFID) elements.

[0007] Accordingly, a need exists for improved methods and structures for forming integrated programmable conductor memory arrays.

SUMMARY OF THE INVENTION

[0008] An integrated programmable conductor memory cell and diode device in an integrated circuit is provided. The device comprises at least a first diode element, a glass electrolyte element over the first diode element, and a top electrode in contact with the glass electrolyte element. The glass electrolyte element has metal ions mixed or dissolved therein and is able to selectively form a conductive pathway under the influence of an applied voltage.

[0009] In accordance with one aspect of the present invention, a memory device, comprising an integrated diode and programmable conductor memory cell is provided wherein both the diode and the memory cell comprise a chalcogenide glass.

[0010] In one embodiment, an integrated programmable conductor memory cell and diode device is provided. The device comprises a first polysilicon layer with a first conductivity type doping, a layer of germanium selenide glass containing metal ions over the first polysilicon layer and a top electrode over the layer of germanium-selenide glass. The device can further comprise a silicon substrate region having a second conductivity type doping, opposite to the first conductivity type doping, wherein the silicon substrate region is in direct contact with the first polysilicon layer.

[0011] In accordance with another aspect of the invention, a method of fabricating a PCRAM (programmable conductor random access memory) is provided. The method comprises forming an insulating layer with an array of vias, providing at least one diode element in each via and providing a chalcogenide glass-memory element over the diode element in each via. The chalcogenide glass memory element has metal ions therein and is capable of selectively forming a conductive pathway under the influence of an applied voltage.

[0012] In yet another aspect of the invention, a method for making a PCRAM cell with an integrated thin film diode in a via is provided. The method comprises providing a diffusion barrier material at a bottom of the via, depositing a first chalcogenide glass to fill the via, etching the first chalcogenide glass back to form a recess in the via, doping the first chalcogenide glass to a predetermined depth after etching, forming a mixture of a second chalcogenide glass and a first conductive material to fill the via after doping and depositing a second conductive material over the mixture.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013] These and other aspects of the invention will be readily understood by the skilled artisan in view of the detailed description of the preferred embodiments below and the appended drawings, which are meant to illustrate and not to limit the invention, and in which:

[0014]FIG. 1 is a cross section of a partially fabricated integrated circuit, showing a via in a silicon nitride layer over a bottom conducting line.

[0015]FIG. 2 shows the via of FIG. 1 after filling the via with germanium selenide (Ge—Se) glass.

[0016]FIG. 3 shows the filled via of FIG. 2 after etching back to recess the Ge—Se glass into the via.

[0017]FIG. 4 shows the Ge—Se glass in the via of FIG. 3 after ion implanting to dope a top portion of the Ge—Se layer.

[0018]FIG. 5 shows the Ge—Se layer of FIG. 4 after an additional layer of Ge—Se glass has been deposited to fill the via.

[0019]FIG. 6A shows the filled via of FIG. 5 after planarization to make the Ge—Se and the surrounding silicon nitride coplanar and subsequent metal deposition and patterning to make a top electrode, in accordance with one embodiment of the present invention.

[0020]FIG. 6B shows the structure of FIG. 6A after formation of a top conductor.

[0021]FIG. 7A shows the filled via of FIG. 5 after deposition of a metal layer over the Ge—Se glass, in accordance with another embodiment of the present invention.

[0022]FIG. 7B shows the structure of FIG. 7A after patterning and etching the metal layer and the Ge—Se overlayer.

[0023]FIG. 7C shows the structure of FIG. 7B after formation of a top conducting line.

[0024]FIG. 8 is a cross section showing another embodiment of the invention wherein an integrated programmable conductor memory cell and diode device comprises a Ge—Se doped layer extending down to a bottom conducting line and overlaid by an undoped layer of Ge—Se glass.

[0025]FIG. 9 is a cross section showing another embodiment of the invention wherein a diode comprises a p⁺ polysilicon layer and an n⁺ polysilicon layer, integrated with a programmable conductor memory cell.

[0026]FIG. 10 is a cross section showing another embodiment of the invention wherein two integrated programmable conductor memory cell and diode devices are shown. A silicon nitride layer having two vias has been formed directly on a silicon substrate. The diodes comprise the underlying p⁺ region of the substrate and n⁺ polysilicon layers at the bottom of the vias.

[0027]FIG. 11 is a cross section showing an alternative arrangement of the embodiment of FIG. 10 wherein first n⁺ polysilicon layers are formed in contact with an underlying p⁺ region of the substrate, and then narrower programmable conductor memory cells are formed in vias in a silicon nitride layer to land on the top surfaces of the diode structures.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0028] A simple diode comprises two diode elements, or sides of opposite conductivity type, in contact with each another, which form a p-n junction at their interface. More complex structures can be made from multiple diode elements.

[0029] It is desirable to have a diode connected in series with each memory cell in an array. This allows for discrete switching of the memory cell as a certain level of forward bias is needed to overcome the diode barrier. Above that voltage, current flows easily through the diode. This diode barrier prevents accidental switching of the memory element. It is further desirable that the diode be “leaky,” that is, that it allow a small amount of conduction when reverse biased to allow a trickle current for reading the memory cell state.

[0030] For the purpose of this disclosure, an integrated programmable conductor memory cell and diode device is defined as a device that incorporates both a programmable conductor memory cell and a diode so that they function together, without intervening electrical devices or lines, although layers such as optional diffusion barriers (described below) can intervene. Several embodiments are discussed comprising various configurations wherein a programmable conductor memory cell and diode elements are arranged to perform this function.

[0031] The aforementioned needs are satisfied by the preferred embodiments of the present invention, which provide integrated programmable conductor memory cells and diode devices and methods for making the same. The advantages of the embodiments will become more fully apparent from the following description taken in conjunction with the accompanying drawings.

[0032] Reference will now be made to the drawings wherein like numerals refer to like parts throughout. The figures have not been drawn to scale.

[0033] A programmable conductor memory element comprises a glass electroltyte element, such as a chalcogenide glass element with metal ions mixed or dissolved therein, which is capable of forming a conductive pathway along or through the glass element under the influence of an applied voltage. The extent of the conductive pathway depends upon applied voltage and time, the higher the voltage, the faster the growth rate; and the longer the time, the greater the extent of the conductive pathway. The conductive pathway stops growing when the voltage is removed. The conductive pathway shrinks, re-dissolving metal ions into the cell body, when the voltage polarity is reversed.

[0034]FIG. 1 is a cross-section drawing showing a structure for a portion of a memory array from which many embodiments of the current invention can be constructed. A bottom conducting line 10 overlies a substrate 8. The substrate 8 may be a simple silicon wafer or it may contain up to several layers of integrated circuit devices and insulating layers; typically, an insulating layer intervenes between the conducting line 10 of a cross-point array and a lower semiconductor layer (e.g., top portion of a silicon wafer or an epitaxial layer thereover). The bottom conducting line 10 extends from side to side in the plane of the page and continues on past the edges of the page. For the memory array, there are a series of conducting lines parallel to the one 10 shown lying over the substrate 8. The bottom conducting line 10 may comprise any conducting material suitable for integrated circuit manufacture, such as aluminum, copper, or combinations thereof. Preferably, the bottom conducting line 10 comprises tungsten and acts as a bottom electrode for devices that will be fabricated over and in contact with the line 10. In one arrangement, an additional layer (not shown) comprising a diffusion barrier, preferably tungsten or tungsten nitride, is deposited over the bottom conducting line 10.

[0035] A layer of an insulating material 12 has been deposited over the bottom conducting line 10. Preferably, the insulating layer 12 has a thickness between about 25 nm and 150 nm, more preferably between about 35 nm and 75 nm, most preferably, between about 40 nm and 60 nm. The insulating material 12 may be any insulating material that does not interact adversely with the materials used in the programmable conductor memory cell and that has enough structural integrity to support a cell formed in a via therein. Suitable materials include oxides and nitrides. Preferably, the insulating layer 12 comprises silicon nitride. Using standard techniques, an array of vias is patterned and etched into the insulating layer 12. The vias are positioned so that their bottom surfaces expose a bottom conducting line (or a diffusion barrier layer thereover). One via 14 that exposes the bottom conducting line 10 is shown in FIG. 1. The width of the via 14 is preferably between about 100 nm and 180 nm, more preferably between about 120 nm and 140 nm. It is in vias such as the one shown in FIG. 1 that the programmable conductor memory cells of many preferred embodiments can be constructed.

[0036]FIG. 2 shows the structure of FIG. 1 after deposition of a chalcogenide glass 16, preferably a germanium selenide (Ge—Se) glass, such as Ge₂Se₈ or Ge₂₅Se₇₅, to overfill the via 14. The chalcogenide glass may be deposited by any of a number of methods including sputtering and evaporating.

[0037] As shown in FIG. 3, the chalcogenide glass layer 16 is etched back to form a recess in the via 14, leaving only a portion 18 of chalcogenide glass remaining in the via 14. The chalcogenide glass is etched back using an isotropic etch, such as a CF₄ dry etch or a tetramethyl ammonium hydroxide (TMAH) wet etch.

[0038]FIG. 4 shows the structure of FIG. 3 after doping a layer 20 of the chalcogenide glass portion 18 in the via 14 to a predetermined depth. In one embodiment, the depth of the doped layer 20 is between about 10 nm and 20 nm. Preferably, doping comprises processing at a temperature less than about 340° C. and to a concentration of between about 0.1 atomic % and 1.0 atomic %. More preferably, doping comprises ion implantation with a species such as bismuth or lead. In the illustrated embodiment, the ion implantation is performed at an energy between about 20 keV and 30 keV at a dose between about 1×10¹³ atoms/cm² and 1×10¹⁴ atoms/cm².

[0039] Germanium-selenium or germanium selenide (also referred to as “Ge—Se” herein) is a p-type semiconductor. Doping germanium selenide with bismuth or lead changes the conductivity from p-type to n-type. Thus in the structure of FIG. 4, the bottom, undoped germanium selenide portion 18 and the doped layer 20 have opposite conductivity types and comprise a p-n junction diode.

[0040] In FIG. 5, another chalcogenide glass layer 22 has been deposited, overfilling the via. This layer 22 forms a programmable conductor memory cell and preferably comprises a germanium selenide glass, such as Ge₂Se₈ or Ge₂₅Se₇₅, with a conductive material, such as metal ions, preferably silver ions, mixed or dissolved therein. In one embodiment, the layer 22 is formed by co-sputtering Ge—Se glass, such as from a pressed powder target, and silver. In other embodiments the Ge—Se glass may be deposited first and then the silver ions diffused therein, such as by photodissolution, as is known in the art of programmable conductor memory cell fabrication. Preferably, the concentration of silver in the chalcogenide glass memory element is between about 20 atomic % and 32 atomic %, more preferably, between about 29 atomic % and 31 atomic %. The skilled artisan can, however, arrive at a desired ratio within or outside these ranges through routine experimentation.

[0041] There are two illustrated embodiments for completing the integrated programmable conductor memory cell and diode device as described thus far. One embodiment is shown in FIGS. 6A-6B. The other is shown in FIGS. 7A-7C.

[0042] In FIG. 6A, the structure of FIG. 5 has been planarized, leaving a programmable conductor chalcogenide glass memory element 24 with metal ions mixed or dissolved therein filling the recess in the via and level with the top surface of the insulating layer 12. A layer of a conducting material, preferably from Group IB or Group IIB, more preferably, silver, has been deposited over the chalcogenide glass element 24 and the insulating layer 12. Preferably, the thickness of the conducting layer is between about 50 nm and 100 nm. The conducting layer has been patterned and etched using standard methods to form a top electrode 26 for the integrated programmable conductor memory cell and diode device. In one aspect of the invention, a diffusion barrier (not shown), such as tungsten nitride, is deposited over the chalcogenide glass element 24 before forming the top electrode 26. A diffusion barrier may also be deposited over the top electrode 26. Another possibility is that the top electrode 26 is a multi-layered structure that includes a diffusion barrier layer as one of its components.

[0043] In FIG. 6B, another conducting layer has been deposited, patterned and etched to form a top conducting line 28 extending into and out of the plane of the paper. Preferably the top conducting line 28 comprises tungsten and connects a row of integrated programmable conductor memory cell and diode devices in the memory array. Tungsten also has the advantage of acting as a diffusion barrier for chalcogenide glass species.

[0044]FIG. 6B is a cross-section view of an integrated programmable conductor memory cell and diode device in a via that shows the structure of an illustrated embodiment. The device comprises a first diode element 18, having a first conductivity type, a glass electrolyte element 24 having metal ions, such as silver, therein over the first diode element 18 and a top electrode 26 in contact with the glass electrolyte element 24. The structure further comprises a second diode element 20, having a second conductivity type, between the first diode element 18 and the glass electrolyte element 24. In the illustrated embodiment, the diode elements 18, 20 and the programmable conductor memory cell or glass electrolyte element 24 all comprise a chalcogenide glass, such as Ge—Se glass. The first diode element 18 is not intentionally doped and is naturally p-type. The second diode element 20 contains an n-type dopant such as bismuth or lead. Preferably there is a diffusion barrier layer (not shown) comprising titanium between the second diode element 20 and the glass electrolyte element 24. The first diode element 18 is in electrical contact with the bottom conducting line 10. A portion of the bottom conducting line 10 that is directly below and in electrical contact with the first diode element 18 forms a bottom electrode for the integrated programmable conductor memory cell and diode device.

[0045] There may also be a diffusion barrier layer (not shown) below the first diode element 18 and a diffusion barrier layer over the chalcogenide glass element 24. In one embodiment, the thickness of the diffusion barrier layer is between about 10 nm and 40 nm. Materials for the diffusion barrier layers include titanium, tungsten and tungsten nitride.

[0046] In the second illustrated embodiment for completing the structure of FIG. 5, as shown in FIG. 7A, a layer of a conducting material 30, preferably from Group IB or Group IIB, more preferably silver, has been deposited over the chalcogenide glass layer 22. Preferably, the thickness of the conducting layer is between about 50 nm and 100 nm. In FIG. 7B, both the conducting layer and the chalcogenide glass layer have been patterned and etched to form a programmable conductor chalcogenide glass memory element 32 with metal ions mixed or dissolved therein and an electrode 34 for the integrated programmable conductor memory cell and diode device.

[0047] In FIG. 7C, another conducting layer has been deposited, patterned and etched to form a top conducting line 28 extending into and out of the plane of the page. Preferably the top conducting line 28 comprises tungsten and connects a row of integrated programmable conductor memory cell and diode devices in the memory array.

[0048]FIG. 7C is a cross-section view of an integrated programmable conductor memory cell and diode device in a via that shows the structure of an illustrated embodiment. The device comprises a first diode element 18, having a first conductivity type, a glass electrolyte element 32 having metal ions, such as silver, mixed or dissolved therein over the first diode element 18 and a top electrode 34 in contact with the glass electrolyte element 32. The structure further comprises a second diode element 20, having a second conductivity type, between the first diode element 18 and the glass electrolyte element 32. In one embodiment, the diode elements 18, 20 and the programmable conductor memory cell or glass electrolyte element 32 all comprise a chalcogenide glass, such as Ge—Se glass. The first diode element 18 is not intentionally doped, and is naturally p-type. The second diode element 20 contains an n-type dopant such as bismuth or lead. Preferably there is a diffusion barrier layer (not shown) comprising titanium between the second diode element 20 and the glass electrolyte element 24.

[0049] There may also be a diffusion barrier layer (not shown) below the first diode element 18 and a diffusion barrier layer over the chalcogenide glass element 32. In one embodiment, the thickness of the diffusion barrier layer is between about 10 nm and 40 nm. Materials for the diffusion barrier layers include titanium, tungsten and tungsten nitride.

[0050] In another embodiment of the current invention and with reference again to FIG. 4, the entire thickness of the chalcogenide glass portion 18 is doped. This embodiment is shown in FIG. 8. The doped chalcogenide glass layer 36 extends down to the bottom conducting line 10 or a diffusion barrier layer thereover (not shown) and forms the first diode element. Hereinafter, processing proceeds much as described for the embodiment in FIGS. 5, 6A and 6B.

[0051] Another chalcogenide glass layer is deposited, overfilling the via. The structure is planarized, leaving the chalcogenide glass layer 38 with metal ions therein filling the recess in the via and level with the top surface of the insulating layer 12. This layer 38 functions both as the second diode element in contact with the first diode element 36 and as the programmable conductor memory element and preferably comprises a germanium selenide glass, such as Ge₂Se₈ or Ge₂₅Se₇₅, with a conductive material, such as metal ions, preferably silver ions, mixed or dissolved therein. A layer of a conducting material, preferably from Group IB or Group IIB, more preferably, silver, is deposited over the chalcogenide glass element 38 and the insulating layer 12. Preferably, the thickness of the conducting layer is between about 50 nm and 100 nm. Using standard methods, the conducting layer is patterned and etched to form a top electrode 26 for the integrated programmable conductor memory cell and diode device.

[0052] In one aspect of the invention, a diffusion barrier (not shown), such as tungsten nitride, is deposited over the chalcogenide glass element 38 before forming the top electrode 26. Alternatively, a diffusion barrier may be deposited over the top electrode 26. Another possibility is that the top electrode 26 is a multi-layered structure that includes a diffusion barrier layer as one of its components. A second conducting layer is deposited, patterned and etched to form a top conducting line 28 extending into and out of the plane of the page. Preferably the top conducting line 28 comprises tungsten and connects a row of integrated programmable conductor memory cell and diode devices in the memory array. Tungsten also has the advantage of acting as a diffusion barrier for chalcogenide glass species.

[0053]FIG. 8 is a cross-section view of an integrated programmable conductor memory cell and diode device in a via that shows the structure of an illustrated embodiment. The integrated PCRAM (memory and diode device) 36, 38 is formed in a via in an insulating layer 12, preferably silicon nitride. A conducting line 10 comprising a metal such as tungsten, extends along the bottom of the via and off the edges of the page. There may be first diffusion barrier layer (not shown) between the conducting line 10 and the first layer of chalcogenide glass 36.

[0054] The first layer of chalcogenide glass 36 has n-type doping from a dopant such as bismuth or lead. A second layer of chalcogenide glass 38, infused with silver, is in contact with the first layer of chalcogenide glass 36. In one arrangement, the chalcogenide glass is Ge₂Se₈ or Ge₂₅Se₇₅. The two layers 36, 38 comprise a p-n junction, and the second layer 38 functions also as a programmable conductor memory element. A top electrode layer 26 lies over the second chalcogenide glass layer 38 and may comprise silver. A conducting line 28, extending into and out of the page is in contact with the electrode 26. In one aspect of the invention, the conducting line 28 comprises tungsten and acts also as a diffusion barrier. In another aspect of the invention, a separate diffusion barrier layer (not shown) is used either below or above the electrode 26. Another embodiment of the invention can be described starting with the structure of FIG. 1. As discussed above, a bottom conducting line 10 overlies a substrate 8. Using standard techniques, an array of vias is patterned and etched into the insulating layer 12. One via 14 is shown in FIG. 1. It is in this via that the programmable conductor memory cell of this embodiment will be constructed.

[0055] With reference to FIG. 9, a layer of tungsten silicide 40 is deposited at the bottom of the via. A first diode element 42, preferably comprising a doped polysilicon layer having a first type conductivity, is deposited over the tungsten silicide layer 40. A second diode element 44, preferably comprising a doped polysilicon layer having a second type conductivity, opposite to the first type conductivity, is deposited over the first diode element 42. The two polysilicon layers 42, 44, having opposite conductivity types, form a polysilicon diode.

[0056] A diffusion barrier layer 46, preferably comprising tungsten nitride, is deposited over the second diode element 44. A chalcogenide glass element 48, preferably a germanium selenide glass with metal ions, preferably silver ions, mixed or dissolved therein, is formed by depositing the glass over the diffusion barrier layer 46 and then planarizing the glass layer to make it level with the top surface of the insulating layer 12. A layer of a conducting material, preferably from Group IB or Group IIB, more preferably, silver, has been deposited over the chalcogenide glass element 48 and the insulating layer 12. Preferably, the thickness of the conducting layer is between about 50 nm and 100 nm. The conducting layer has been patterned and etched using standard methods to form a top electrode 26 for the integrated programmable conductor memory cell and polysilicon diode device. Preferably a diffusion barrier (not shown), more preferably, tungsten nitride, is deposited over the chalcogenide glass element 48 before forming the top electrode 26. Finally, although not shown in FIG. 9, a conducting line may be provided as described above with reference to FIGS. 6B and 7C.

[0057]FIG. 9 is a cross-section view of an integrated programmable conductor memory cell and diode device that shows the structure of an illustrated embodiment. The first polysilicon layer 42, having a first conductivity type doping, lies in a via in an insulating layer 12. There is a second polysilicon layer 44, having a second conductivity type doping, opposite to the first conductivity type, between the first polysilicon layer 42 and a diffusion barrier layer 46. For example, the first polysilicon layer 42 may have p-type doping, and the second polysilicon layer 44 may have n-type doping. There is a layer of germanium selenide glass 48, containing metal ions, over the diffusion barrier layer 46. There is a top electrode 26 over the germanium selenide glass 48. The top electrode 26 may comprise both a conducting layer and a diffusion barrier layer.

[0058] Another aspect of the invention can be described with reference to FIG. 10. A silicon substrate 8 is shown with a region 52 doped to have a first type conductivity, preferaby p⁺. The region 52 forms the first diode element.

[0059] A layer of an insulating material 12 has been deposited over the substrate 8. Preferably the insulating layer 12 has a thickness between about 50 nm and 150 nm, more preferably between about 95 nm and 105 nm. The insulating material 12 may be any insulating material that does not interact adversely with the materials used in the programmable conductor memory cell or in the diode and that has enough structural integrity to support a cell formed in a via therein. Suitable materials include oxides and nitrides. Preferably the insulating layer 12 comprises silicon nitride. Using standard techniques, an array of vias is patterned and etched into the insulating layer 12. Two such vias, containing integrated programmable conductor memory cell and diode devices are shown in FIG. 10.

[0060] A polysilicon layer 54, having a second conductivity type, preferably n⁺, opposite to the first conductivity type of the doped region 52, is deposited into the via in contact with the doped region 52 of the substrate 8. Polysilicon layer 54 forms the second diode elements and, together with doped region 52, forms p-n junction diodes.

[0061] Diffusion barrier layers 56, preferably comprising tungsten nitride, are deposited over the second diode elements 54. Chalcogenide glass elements 58, preferably germanium selenide glass with metal ions, preferably silver ions, mixed or dissolved therein, are formed by depositing the glass over the diffusion barrier layers 56 and then planarizing the glass to make it level with the top surface of the insulating layer 12. A layer of a conducting material, preferably from Group IB or Group IIB, more preferably, silver, is deposited over the chalcogenide glass elements 58 and the insulating layer 12. Preferably, the thickness of the conducting layer is between about 50 nm and 100 nm. The conducting layer is patterned and etched using standard methods to form top electrodes 26 for the integrated programmable conductor memory cell and polysilicon diode devices 58, 52, 54. Preferably a diffusion barrier (not shown), more preferably, tungsten nitride, is deposited over the chalcogenide glass elements 58 before forming the top electrodes 26.

[0062] A conducting line 28, extending into and out of the page, is in contact with the electrode 26. A conductive plug 60, preferably comprising polysilicon or a metal such as tungsten, makes contact to the doped silicon substrate region 52 and to conducting line 62, thus providing electrical connections for the integrated programmable conductor memory cell and diode device of FIG. 10. Conducting line 62 is insulated from conducting line 28 by layer 64, preferably comprising BPSG (borophosphosilicate glass).

[0063] Another aspect of the invention can be described with reference to FIG. 11. A silicon substrate 8 is shown with a region 52 doped to have a first conductivity type, preferably p⁺. The region 52 forms the first diode elements for integrated programmable conductor memory cell and diode devices.

[0064] A layer of polysilicon with conductivity, preferably n⁺, opposite to the conductivity of the doped region 52 of the substrate 8 is deposited. The polysilicon layer is patterned and etched to form the second diode elements 54. Preferably, a diffusion barrier layer, such as tungsten, tungsten nitride or titanium, is deposited onto the polysilicon layer and then patterned and etched with the polysilicon layer, thus forming diffusion barrier layers 56 over the second diode elements 54.

[0065] A layer of material 64, preferably silicon nitride, is deposited conformally onto the second diode elements 54 and diffusion barrier layers 56 to act as an etch stop for a subsequent chemical-mechanical planarization step. An insulating layer 66, preferably comprising silicon oxide formed from TEOS, is deposited to a thickness that at least covers the top surface of layer 64. Chemical-mechanical planarization is performed until the top portions of layer 64 are exposed to make a flat top surface for silicon oxide layer 66. The exposed portions of layer 64 are patterned and etched to expose at least a portion of a top surface of the diffusion barrier layer 56.

[0066] A layer of insulating material 12, preferably silicon nitride, is deposited over the silicon oxide layer 66. The layer 12 is patterned and etched to form vias down through layer 64 and onto diffusion barrier layer 56. A chalcogenide glass layer is deposited, overfilling the vias. The chalcogenide glass forms the programmable conductor memory cells 58 and preferably comprises a germanium selenide glass, such as Ge₂Se₈ or Ge₂₅Se₇₅, with a conductive material, such as metal ions, preferably silver ions, mixed or dissolved therein. In one embodiment, the glass is formed by co-sputtering Ge—Se glass, such as from a pressed powder target, and silver. In other embodiments the Ge—Se glass may be deposited first and then the silver ions diffused therein, such as by photodissolution, as is known in the art of programmable conductor memory cell fabrication. Preferably, the concentration of silver in the chalcogenide glass memory element is between about 20 atomic % and 36 atomic %, more preferably, between about 29 atomic % and 32 atomic %.

[0067] A layer of a conducting material 27, preferably from Group IB or Group IIB, more preferably silver, is deposited over the chalcogenide glass layer 58. Preferably, the thickness of the conducting layer is between about 50 nm and 100 nm. Both the conducting layer 27 and the chalcogenide glass layer 58 are patterned and etched to form programmable conductor chalcogenide glass memory elements 58 with metal ions mixed or dissolved therein and electrodes and conducting lines 27 for the memory cells 58.

[0068] A layer of insulating material 64, preferably comprising BPSG (borophosphosilicate glass), is deposited over the conducting lines 27 and planarized. A via is etched through insulating layers 64, 12 and 66, down to expose a portion of the doped region 52 of the substrate 8. The via is filled with conducting material, preferably polysilicon or a metal such as tungsten, thus forming a conductive plug 60 that makes contact to the doped silicon substrate region 52. A conductive line, preferably comprising aluminum or copper, is formed over the BPSG 64 and makes contact with the conductive plug 60, and thus to the diodes in the integrated programmable conductor memory cell and diode devices.

[0069] This invention has been described herein in considerable detail to provide those skilled in the art with the information needed to apply the novel principles and to construct and use such specialized components as are required. However, it is to be understood that the invention can be carried out by specifically different equipment and devices, and that various modifications, both as to the structure and as to the method of fabricating the structure, can be accomplished without departing from the scope of the invention itself. 

I claim:
 1. An integrated programmable conductor memory cell and diode device in an integrated circuit, comprising: a first diode element; a glass electrolyte element over the first diode element, the glass electrolyte element having metal ions therein and being able to selectively form a conductive pathway under the influence of an applied voltage; and a top electrode in contact with the glass electrolyte element.
 2. The integrated programmable conductor memory cell and diode device of claim 1, wherein the glass electrolyte element is a second diode element.
 3. The integrated programmable conductor memory cell and diode device of claim 1, wherein the first diode element comprises a chalcogenide glass layer having a first conductivity type, and the glass electrolyte element has a second conductivity type opposite to the first conductivity type, is in direct contact with the first diode element and thus forms a second diode element.
 4. The integrated programmable conductor memory cell and diode device of claim 1, further comprising a barrier layer between the first diode element and the glass electrolyte element, wherein the first diode element comprises silicon having a first conductivity type, and the first diode element is in direct contact with a doped silicon substrate region having a second conductivity type opposite to the first conductivity type, the doped silicon substrate region forming a second diode element.
 5. The integrated programmable conductor memory cell and diode device of claim 1, further comprising a second diode element between the first diode element and the glass electrolyte element.
 6. The integrated programmable conductor memory cell and diode device of claim 5, wherein the glass electrolyte element and at least one diode element are within a via.
 7. The integrated programmable conductor memory cell and diode device of claim 6, wherein the glass electrolyte element and both diode elements are within a via.
 8. The integrated programmable conductor memory cell and diode device of claim 5, wherein the first diode element comprises a chalcogenide glass having a first conductivity type and the second diode element comprises a chalcogenide glass having a second conductivity type opposite to the first conductivity type.
 9. The integrated programmable conductor memory cell and diode device of claim 5, further comprising a diffusion barrier layer between the second diode element and the glass electrolyte element, wherein the first diode element comprises silicon having a first conductivity type and the second diode element comprises silicon having a second conductivity type opposite to the first conductivity type.
 10. The integrated programmable conductor memory cell and diode device of claim 1, wherein the glass electrolyte element is within a via.
 11. The integrated programmable conductor memory cell and diode device of claim 10, wherein the glass electrolyte element within the via is landed on the first diode element.
 12. The integrated programmable conductor memory cell and diode device of claim 11, wherein the first diode element comprises silicon having a first conductivity type and is in direct contact with a doped silicon substrate region having a second conductivity type opposite to the first conductivity type, the doped silicon substrate region forming a second diode element.
 13. A memory device, comprising an integrated diode and programmable conductor memory cell wherein both the diode and the memory cell comprise a chalcogenide glass.
 14. The memory device of claim 13, comprising: a first chalcogenide glass element over a first diffusion barrier layer in a bottom portion of a via; a second chalcogenide glass element having n-type doping and overlying the first chalcogenide glass element; a third chalcogenide glass element containing silver and overlying the second chalcogenide glass element; a second diffusion barrier layer over the third chalcogenide glass element.
 15. The integrated programmable conductor memory cell and diode of claim 14, wherein the first diffusion barrier layer is selected from the group consisting of tungsten and tungsten nitride.
 16. The integrated programmable conductor memory cell and diode of claim 14, wherein the first chalcogenide glass element comprises a germanium selenide glass.
 17. The integrated programmable conductor memory cell and diode of claim 14, wherein the second chalcogenide glass element having n-type doping comprises a dopant selected from the group consisting of bismuth and lead.
 18. The integrated programmable conductor memory cell and diode of claim 17, wherein the dopant comprises between about 0.1 atomic % and 1.0 atomic % of the second chalcogenide glass element.
 19. The integrated programmable conductor memory cell and diode of claim 17, wherein the second chalcogenide glass element is between about 10 nm and 20 nm in thickness.
 20. The integrated programmable conductor memory cell and diode of claim 17, wherein an interface between the second chalcogenide glass element and the underlying first chalcogenide glass element comprises a p-n junction.
 21. The integrated programmable conductor memory cell and diode of claim 14, wherein the third chalcogenide glass element comprises between about 20 atomic % and 32 atomic % silver
 22. The integrated programmable conductor memory cell and diode of claim 21, wherein the third chalcogenide glass element comprises between about 29 atomic % and 31 atomic % silver.
 23. The integrated programmable conductor memory cell and diode of claim 14, further comprising a layer of conducting material as a top electrode between the third chalcogenide glass element and the second diffusion barrier layer.
 24. The integrated programmable conductor memory cell and diode of claim 23, wherein the layer of conducting material as a top electrode comprises silver.
 25. A PCRAM cell with an integrated diode, comprising: a first layer of chalcogenide glass with n-type doping over the first diffusion barrier layer; a second layer of chalcogenide glass infused with silver and in contact with the first layer of chalcogenide glass; and a top electrode layer over the second layer of chalcogenide glass, the top electrode layer comprising silver.
 26. The PCRAM cell of claim 25, wherein the first diffusion barrier layer and the second diffusion barrier layer both comprise materials selected from the group consisting of tungsten and tungsten nitride.
 27. The PCRAM cell of claim 25, wherein sides of the PCRAM cell and the diode are surrounded by a silicon nitride layer.
 28. The PCRAM cell of claim 25, wherein the first layer of chalcogenide glass with n-type doping comprises germanium selenide doped with bismuth.
 29. The PCRAM cell of claim 25, wherein the second layer of chalcogenide glass comprises germanium selenide.
 30. The PCRAM cell of claim 25, wherein an interface between the first layer of chalcogenide glass and the second layer of chalcogenide glass comprises a p-n junction.
 31. An integrated programmable conductor memory cell and diode device comprising: a first polysilicon layer with a first conductivity type doping; a layer of germanium selenide glass containing metal ions over the first polysilicon layer; and a top electrode over the layer of germanium selenide glass.
 32. The integrated programmable conductor memory cell and diode device of claim 31, further comprising a silicon substrate region having a second conductivity type doping, opposite to the first conductivity type doping, wherein the silicon substrate region is in direct contact with the first polysilicon layer.
 33. The integrated programmable conductor memory cell and diode device of claim 31, wherein there is a diffusion barrier layer over the first polysilicon layer.
 34. The integrated programmable conductor memory cell and diode device of claim 31, further comprising a second polysilicon layer with a second conductivity type doping, opposite to the first conductivity type, between the first polysilicon layer and the diffusion barrier layer.
 35. The integrated programmable conductor memory cell and diode device of claim 34, wherein the first polysilicon layer has p-type doping, and the second polysilicon layer has n-type doping.
 36. The integrated programmable conductor memory cell and diode device of claim 31, wherein the top electrode comprises a conducting layer and a diffusion barrier layer.
 37. A method of fabricating memory cells for a memory array in an integrated circuit, comprising: forming a bottom electrode having electrical contact to a conductive region in a semiconductor base material; providing a first diode element having a first conductivity type and having electrical contact to the bottom electrode; forming a glass electrolyte layer over the first diode element, the glass electrolyte layer having metal ions therein and being capable of growing a conductive pathway under the influence of an applied voltage; and forming a top electrode over the glass electrolyte layer.
 38. The method of claim 37, wherein providing a first diode element comprises depositing and doping a layer of chalcogenide glass.
 39. The method of claim 38, wherein forming the glass electrolyte layer comprises providing a second diode element having a second conductivity type opposite to the first conductivity type.
 40. The method of claim 37, further comprising, between the steps of providing a first diode element and forming a glass electrolyte layer, providing a second diode element having a second conductivity type opposite to the first conductivity type.
 41. The method of claim 40, wherein providing the first diode element comprises providing a doped region in the semiconductor base material having a first conductivity type, and providing the second diode element comprises depositing and doping a polysilicon layer having a second conductivity type opposite to the first conductivity type.
 42. The method of claim 40, wherein providing the first and the second diode elements comprises providing two doped polysilicon layers having opposite conductivity types.
 43. The method of claim 40, wherein providing the first and the second diode elements comprises depositing a layer of chalcogenide glass having a first conductivity type and doping a top portion of the layer of chalcogenide glass to transform the top portion to a second conductivity type opposite to the first conductivity type.
 44. The method of claim 37, further comprising providing diffusion barrier layers above and below the glass electrolyte layer.
 45. A method of fabricating a programmable conductor random access memory (PCRAM), comprising: forming an insulating layer with an array of vias, each via having a bottom surface; providing at least one diode element in each via; and providing a chalcogenide glass memory element over the diode element and in each via, the chalcogenide glass memory element having metal ions therein and capable of selectively forming a conductive pathway through or along the chalcogenide glass memory element under the influence of an applied voltage.
 46. The method of claim 45, wherein forming an insulating layer with an array of vias comprises etching vias in a layer of silicon nitride.
 47. The method of claim 45, wherein a thickness of the insulating layer is between about 80 nm and 120 nm.
 48. The method of claim 45, wherein the thickness of the insulating layer is between about 95 nm and 105 nm.
 49. The method of claim 45, wherein the via is between about 180 nm and 250 nm in width.
 50. The method of claim 45, wherein the bottom surface of the via comprises a doped region of a semiconductor substrate having a first type conductivity.
 51. The method of claim 52, wherein providing at least one diode layer comprises depositing a polysilicon layer having a second type conductivity, opposite to the first type conductivity, the polysilicon layer having direct contact with the doped region of the semiconductor substrate.
 52. The method of claim 45, wherein the bottom surface of the via comprises a metal conductor.
 53. The method of claim 52, wherein providing at least one diode layer comprises depositing two polysilicon layers in contact with one another and doped to have opposite conductivity types.
 54. The method of claim 52, wherein providing at least one diode layer comprises providing a layer of germanium selenide (Ge—Se) glass doped with bismuth.
 55. The method of claim 54, wherein providing at least one diode layer further comprises providing a layer of Ge—Se glass between the layer of Ge—Se glass doped with bismuth and the metal conductor.
 56. The method of claim 55, further comprising providing a layer of tungsten nitride between the bottom surface of the via and the bottommost layer of Ge—Se.
 57. The method of claim 45, wherein providing the chalcogenide glass element with metal ions therein comprises co-sputtering Ge—Se glass and silver.
 58. The method of claim 45, further comprising providing a layer of tungsten nitride over the chalcogenide glass memory element.
 59. The method of claim 58, further comprising depositing a layer of silver over the tungsten nitride.
 60. The method of claim 59, further comprising patterning and etching the layer of silver to form a top electrode.
 61. A method for making a PCRAM cell with an integrated thin film diode in a via, comprising: providing a diffusion barrier material at a bottom of the via; depositing a first chalcogenide glass to fill the via; etching the first chalcogenide glass back to form a recess in the via; doping the first chalcogenide glass to a predetermined depth after etching; forming a mixture of a second chalcogenide glass and a first conductive material to fill the via after doping; and depositing a second conductive material over the mixture.
 62. The method of claim 61, wherein the first chalcogenide glass and the second chalcogenide glass each comprise germanium (Ge) and selenium (Se).
 63. The method of claim 62, wherein the first chalcogenide glass and the second chalcogenide glass comprise Ge₂Se₈ or Ge₂₅Se₇₅.
 64. The method of claim 61, wherein the first chalcogenide glass is deposited by sputtering.
 65. The method of claim 61, wherein the first chalcogenide glass is deposited by evaporating.
 66. The method of claim 61, wherein etching the first chalcogenide glass back comprises an isotropic etch.
 67. The method of claim 66, wherein the isotropic etch comprises a CF₄ dry etch.
 68. The method of claim 66, wherein the isotropic etch is an aqueous base.
 69. The method of claim 66, wherein the isotropic etch comprises tetramethyl ammonium hydroxide (TMAH).
 70. The method of claim 66, wherein the isotropic etch comprised ammonium hydroxide.
 71. The method of claim 61, wherein doping the first chalcogenide glass comprises processing at a temperature less than about 340° C.
 72. The method of claim 71, wherein doping the first chalcogenide glass comprises ion implantation.
 73. The method of claim 72, wherein ion implantation comprises a species selected from the group consisting of bismuth and lead.
 74. The method of claim 73, wherein ion implantation is performed at an energy between about 20 keV and 30 keV at a dose between about 1×10¹³ atoms/cm² and 1×10¹⁴ atoms/cm².
 75. The method of claim 71, wherein doping the first chalcogenide glass to a predetermined depth comprises doping to a depth of between about 10 nm and 20 nm, thereby forming a p-n junction with the underlying chalcogenide glass.
 76. The method of claim 71, wherein doping the first chalcogenide glass to a predetermined depth comprises doping through the entire depth of the chalcogenide glass, thereby forming a p-n junction at the boundary of the first, doped chalcogenide glass and the mixture of the second chalcogenide glass and the first conductive material.
 77. The method of claim 61, wherein forming the mixture of the second chalcogenide glass and the first conductive material comprises co-sputtering germanium selenide from a pressed powder target and silver from a silver target.
 78. The method of claim 61, wherein depositing the second conductive material over the mixture of the second chalcogenide glass and the first conductive material comprises depositing a layer of second conductive material selected from the group consisting of Group IB or Group IIB metals to a thickness of about 50 nm to about 100 nm.
 79. The method of claim 78, wherein both the first conductive material and the second conductive material comprise silver.
 80. The method of claim 79, further comprising patterning the silver layer to form a top electrode for the PCRAM cell.
 81. The method of claim 80, further comprising providing conducting lines, in contact with the top electrode for the PCRAM cell and providing connections to other PCRAM cells.
 82. The method of claim 81, wherein the conducting lines comprise tungsten.
 83. A method of fabricating a programmable conductor memory device wherein each memory cell has an ancillary diode, comprising: etching a via in a silicon nitride layer over a tungsten region; filling the via with germanium selenide (Ge—Se); etching back the Ge—Se to form a recess in the via; ion implanting the Ge—Se with bismuth; co-sputtering a mixture of Ge—Se and silver (Ag); depositing and patterning a silver layer onto the mixture of Ge—Se and Ag to form a top electrode; and depositing a top conducting layer of tungsten.
 84. A method of forming a memory cell, comprising: providing a polysilicon diode; forming a diffusion barrier layer over the diode; depositing germanium selenide glass over the diffusion barrier; and infusing the germanium selenide glass with metal ions. 